JPH0841244A - Polymer composition stabilized to ultraviolet light - Google Patents

Abstract

PURPOSE: To obtain a polymer composition excellent in resistance to ultraviolet rays by incorporating a hindered amine, a bisalkyleneaminocyanoacrylate ester and a specified polymer.

CONSTITUTION: There is provided the objective composition comprising (A) a hindered amine such as of formula I (wherein R¹ is a 4-12C alkyl; R² is a 1-5C prim. alkyl; and R³ is a 4-12C alkylene) [for example, bis(1-octyloxy-2,2,6,6- tetramethyl-4-piperidinyl)sebacate], (B) a bis-alkyleneaminocyanoacrylate ester such as a compound of formula II [wherein A is a monocyclic or polycyclic alkane; A¹ is a (substituted) aromatic group; R is a 1-5C alkyl; and R¹ is propylene or butylene], and (C) a polymer being a polycarbonate, a polyester, an acrylic polymer, an ABS copolymer, an acrylonitrile/styrene copolymer, a PVC, a PS, a butyrate or a PE.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel polymer compositions. In particular, the polymer composition of the present invention comprises a hindered amine light stabilizer and an ultraviolet light absorber and exhibits unexpectedly improved resistance to ultraviolet light.

[0002]

BACKGROUND OF THE INVENTION Thermoplastics and blends containing them are generally characterized by a number of advantageous properties including optical clarity, high ductility, high heat deflection temperature and dimensional stability. As a result of these properties, these resins and blends are often used in many commercial applications.

Despite having the advantageous properties described above, thermoplastics and their blends, like many other organic polymeric materials, are susceptible to photolysis by ultraviolet light. This photodegradation usually results in undesirable results, including yellowing and erosion of the polymer / blend surface. There is an increasing need and importance for producing thermoplastics and blends made therefrom that are resistant to photodegradation. Conventionally, in order to produce such resins and blends, the surface of the polymer / blend is usually treated with a coating material containing an ultraviolet light absorber such as cyanoacrylate, benzophenone or a derivative of benzotriazole.

However, when exposed to ultraviolet light, it is often seen that the ultraviolet light absorber itself decomposes. This would degrade the beneficial properties of the polymer / blend originally intended to be protected by the absorbent. Accordingly, the present invention relates to a novel polymer composition that exhibits unexpectedly improved resistance to ultraviolet light, the novel polymer composition comprising a hindered amine light stabilizer and an ultraviolet light absorber. .

Efforts have been made to produce weatherable compositions, and the results have been published. US Pat. No. 5,214,085, assigned to the applicant, incorporates a hindered amine-based compound having a cyclic hindered amino ether moiety into a coating composition, the composition comprising a polycarbonate-based It can be used as a top coat.

[0006] Also, in US Pat. No. 4,636,408, assigned to the applicant, a stabilizing composition containing a hindered amine and a radiation absorber such as benzophenone is impregnated into a polyphenylene ether resin. . Comparing the present invention with the above-mentioned prior art, the present invention is particularly characterized in that it contains a hindered amine light stabilizer and an ultraviolet light absorber and exhibits unexpectedly improved resistance to ultraviolet light. Can be distinguished from the prior art.

[0007]

SUMMARY OF THE INVENTION The present invention relates to novel polymer compositions that exhibit unexpectedly improved resistance to ultraviolet light. The polymer composition of the present invention comprises (a) at least one hindered amine, (b) bis-alkyleneamino cyanoacrylate ester, and (c) polycarbonate, polyester, acrylic polymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer. , A polymer selected from the group consisting of polyvinyl chloride, polystyrene, butyrate and polyethylene.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Suitable hindered amine light stabilizers (hindered piperidyl esters) that can be used in the present invention have the formula I:

[0009]

[Chemical 4]

Wherein R ¹ is C _4-12 alkyl,
R ² is each independently a C _1-5 primary alkyl,
R ³ is C _4-12 alkylene. Such hindered amine light stabilizers can be further characterized as cyclic hindered amino ether derivatives. R in formula I
¹ is n-butyl, n-pentyl, n-hexyl, n-
Primary alkyls such as octyl and n-decyl are preferred. R ² is C _1-4 primary alkyl (ie, methyl, ethyl, n-propyl or n-butyl), with methyl being preferred. R ³ is a C _4-12 alkylene group such as hexamethylene, octamethylene or decamethylene, and octamethylene is preferable. IUP of the compound of formula I when R ¹ is n-octyl, each R ² is methyl and R ³ is octamethylene
AC name is bis (1-octyloxy-2,2,6,6
-Tetramethyl-4-piperidinyl) sebacate, which is commercially available.

The hindered amines used in the present invention do not generally absorb radiation in the ultraviolet or visible region of the spectrum and are therefore not generally considered to be radiation absorbing compounds. The exact mechanism of action is not known, but it is thought that the mechanism of energy quenching and antioxidant action (peroxide decomposition and alkyl group termination) is involved.

The bis-alkyleneaminocyanoacrylate ester used as the ultraviolet light absorber in the present invention is commercially available and can be represented by the following formula II.

[0013]

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Where A is a monocyclic or polycyclic alkane, preferably cyclohexane, A ¹ is each independently a substituted or unsubstituted aromatic group, preferably a phenyl group, and R is Each is independently a C _1-5 alkyl group, preferably hydrogen, and R ¹ is each independently propylene or butylene, preferably methylene.

The polymer compositions of the present invention preferably include polycarbonates, polyesters, acrylonitrile-butadiene-styrene copolymers or blends thereof (especially polycarbonate / polyester blends), although for the polymers which can be used in the present invention, hindered amines and bismuths are preferred. There is no limitation other than being compatible with the -alkyleneamino cyanoacrylate ester. Thus, for example, it is within the scope of the invention to include an acrylic polymer such as poly (methylmethacrylate), acrylonitrile-styrene copolymer, polyvinyl chloride, polystyrene, a blend of polystyrene and polyphenylene ether, butyrate, polyethylene, etc. in the composition. Is.

Preferred polycarbonates for use in the present invention may contain structural units of formula II or III:

[0017]

[Chemical 6]

Formula III is a preferred class of formula II, wherein A ¹ is a divalent substituted or unsubstituted aliphatic, alicyclic or aromatic group, preferably A ² -Y. -A
³ , where A ² and A ³ are each independently a monocyclic divalent aromatic group, and Y is 1 to 4 atoms of A ² and A 3.
It is a bridge that separates the ^three . A ² and A ³ may be unsubstituted phenylene or a substituted derivative thereof, and representative (one or more) substituents include alkyl, alkenyl, alkoxy and the like. Unsubstituted phenylene groups are preferred. It is preferred that both A ² and A ³ are p-phenylene, but both may be o- or m-phenylene, one is o- or m-phenylene and the other is p-phenylene. Good.

The bridging group, Y, is such that one or two atoms, preferably one atom, separate A ² from A ³ . It is a hydrocarbon radical, especially a saturated radical, for example methylene, cyclohexylmethylene, 2- [2.2.
1] -bicycloheptylmethylene, ethylene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene or adamanthylidene, especially gem-alkylene (alkylidene) groups. However, unsaturated groups and groups containing atoms other than carbon and hydrogen, such as 2,
Also included are 2-dichloroethylidene, carbonyl, phthalidylidene, oxy, thio, sulfoxy, sulfone and the like. The preferred unit of formula III is the 2,2-bis (4-phenylene) propanecarbonate unit, which is derived from bisphenol A, because of its ready availability and particular suitability for the present invention, where Y is isopropylamine. In lidene, both A ² and A ³ are p-phenylene.

The origin of the structural units of the above formula II is represented by the following formula IV. HO-A ¹ -OH IV However, A ¹ is as defined above. Non-limiting representatives of Formula IV include: 2,2-bis (4-hydroxyphenyl) propane [ie, bisphenol A], 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane, 2,2-bis (3,3
5-dimethyl-4-hydroxyphenyl) propane,
1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) decane, 1,4-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane, 4,
4-dihydroxydiphenyl ether, 4,4-thiodiphenol, 4,4-dihydroxy-3,3-dichlorodiphenyl ether, 4,4-dihydroxy-3,3-
Dihydroxydiphenyl ether, 1,3-benzenediol, 1,4-benzenediol.

Similarly, other useful dihydroxyaromatic compounds suitable for use in making the above polycarbonate are US Pat. Nos. 2,999,835 and 3,02.
No. 8,365, No. 3,334,154 and No. 4,131,575, all of which are incorporated herein by reference. The preferred bisphenol is 2,2-bis (4-hydroxyphenyl) propane, or bisphenol A.

The polycarbonate used in the present invention (homopolycarbonate or copolycarbonate) may be linear or branched or may be a graft polymer. These can be produced, for example, by reacting the bisphenol with a carbonate source (eg phosgene or dimethyl carbonate) using conventional techniques. Common techniques include melt polymerization, interfacial polymerization, and polymerization followed by interfacial conversion with bischloroformate. Chain terminators such as phenols can also be used.

The polyester used in the present invention is a poly (alkylene dicarboxylate), typically a group consisting of polymeric glycol terephthalates or glycol isophthalates and mixtures thereof, such as copolyesters of terephthalic acid and isophthalic acid. belongs to. The preferred polyester for use in the present invention is poly (1,4-butylene terephthalate).

To produce these polyesters, for example, the cis or trans isomer of 1,4-cyclohexanedimethanol (or a mixture thereof) may be reacted with a mixture of isophthalic acid and terephthalic acid. Such manufacturing methods are well known in the art and are commonly assigned to U.S. Pat. No. 2,901,466 and U.S. Pat. No. 4,125,571, the disclosures of which are hereby incorporated by reference. Are included herein by reference).

The polycarbonate / polyester blends used in the present invention can be produced, for example, in the molten state. During melt mixing, for example, pellets of pure polycarbonate and polyester are heated to a temperature of about 29.
It can be placed in a mixing vessel at 0 ° C. and mixed to obtain the desired blend. The weight ratio of polycarbonate to polyester can be varied within wide limits. For example, it can be about 99: 1 to about 1:99, but is usually about 90:10 to about 10:90, preferably about 75:25 to about 25:75.

Synthetic polymers such as acrylonitrile-butadiene-styrene copolymers (ABS) which can be used in the present invention can be prepared by grafting monomers to a rubbery polymer backbone in a latex. In the case of ABS, acrylonitrile and styrene are often grafted in a latex onto a rubbery polybutadiene and / or a rubbery styrene-butadiene copolymer. Usually, prior to grafting, the latex of rubbery polybutadiene is mixed with the monomer to be grafted onto it and the mixture is agitated for a period of up to several hours to emulsify the monomer and allow the rubbery polymer to remove these monomers. It is common to start the grafting reaction after allowing it to absorb.

The rubbery backbone polymer is usually produced by a process of contacting, for example, butadiene with an alfin type or amyl sodium type catalyst. In particular, polybutadiene latex is butadiene,
It is usually prepared by emulsion polymerization techniques using an aqueous emulsion consisting of an anionic emulsifier and a free radical initiator.

The UV light absorber and the hindered amine used in the present invention are each less than about 2.0% by weight of the total weight of the polymer in the composition, preferably less than about 1.0% by weight. Most preferably, however, each of the ultraviolet light absorber and the hindered amine is less than about 0.6% by weight of the total weight of polymer in the composition. It is also within the scope of the present invention to include conventional additives such as thickeners, pigments, dyes, stabilizers and impact modifiers in the composition of the present invention.

[0029]

DESCRIPTION OF THE EXAMPLES The following examples illustrate the UV light stabilized polymer compositions of the present invention and aid in understanding the manufacture thereof. The molecular structure of the product can be confirmed by proton and carbon-13 nuclear magnetic resonance spectra. Examples Bisphenol A polycarbonate 60.0 parts by weight, poly (1,4-butylene terephthalate) 25.0 parts by weight, methacrylate-butadiene-styrene terpolymer (MBS impact modifier) 10.0 parts by weight, octadecyl 3- (3,5-Di-tert-butyl-4-hydroxyphenol) propionate 0.3 parts by weight, titanium dioxide 3.0 parts by weight, bis (1-octyloxy-2,2,6,6-tetramethyl sebacate) 0.5 parts by weight of (4-piperidinyl) and 0.5 parts by weight of bis-methyleneaminocyanoacrylate ester were mixed and extruded at 290 ° C. to give granules of the polymer composition stabilized against ultraviolet light. Manufactured. Then the granules at 300 ° C
4 ″ of a polymer composition which has been stabilized by heating and molding to
A plate of x8 "x 1/8" was formed.

The data summarized in the following table demonstrate the novel and unexpected superior properties of the compositions of this invention. This new and unexpectedly superior property is the result of the synergistic effect of the hindered amine and the UV absorber in the composition of the present invention. Table 100 300 500 Sample ^A Hindered amine UV absorber Total discoloration after time ^B 1 No No 3.0 3.0 7.9 8.8 2 Yes No 1.0 3.8 4.6 3 Yes Yes 0.67 2.0 All 3.8 ^A samples were prepared as described in the examples.

^B Total discoloration was achieved by placing plates of polymer composition in a Xenotest 1200 instrument for 100 hours, 3 hours.
CIE L after exposure to UV light for 00 hours and 500 hours
Based on the AB test (DIN 6174).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08L 101/00

Claims (21)

[Claims] 1. (a) at least one hindered amine, (b) bis-alkyleneaminocyanoacrylate ester, and (c) polycarbonate, polyester, acrylic polymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, polyvinyl chloride A polymer composition resistant to ultraviolet light, comprising a polymer selected from the group consisting of :, polystyrene, butyrate and polyethylene. 2. The hindered amine has the formula: [Wherein R ¹ is C _4-12 alkyl, R ² is each independently C _1-5 primary alkyl, and R ³ is C _4-12
The polymer composition of claim 1, wherein 3. The polymer composition according to claim 2, wherein the hindered amine is bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate. 4. The bis-alkyleneamino cyanoacrylate ester has the formula: [Wherein A is a monocyclic or polycyclic alkane,
¹ is each independently a substituted or unsubstituted aromatic group, R is each independently a C _1-5 alkyl group, R
¹ is each independently propylene or butylene]
The polymer composition according to claim 1, comprising: 5. The polymer composition according to claim 4, wherein A is cyclohexane, A ¹ is a phenyl group, R is hydrogen and R ¹ is methylene. 6. The polymer composition according to claim 1, wherein the polycarbonate is a homopolycarbonate. 7. The polymer composition according to claim 1, wherein the polycarbonate is a copolycarbonate. 8. The polycarbonate has the formula: The polymer composition according to claim 1, comprising a structural unit of the formula: wherein A ¹ is a divalent substituted or unsubstituted aliphatic group, alicyclic group or aromatic group. 9. A ¹ is A ² —Y—A ³ , A ² and A ³ are each independently a macrocyclic divalent aromatic group and Y is a bridging group. The polymer composition according to claim 8. 10. The polymer composition of claim 9, wherein the polycarbonate is bisphenol A polycarbonate. 11. The polymer composition of claim 1, wherein the polyester is poly (alkylene dicarboxylate). 12. The polymer composition of claim 11, wherein the polyester is poly (1,4-butylene terephthalate). 13. The polymer composition of claim 1, wherein the blend comprises polycarbonate and polyester. 14. The blend comprises from about 99: 1 to about 1: 1.
14. The polymer composition of claim 13, comprising a 99 weight ratio of bisphenol A polycarbonate and poly (1,4-butylene terephthalate). 15. The blend comprises from about 90:10 to about 1.
Consisting of bisphenol A polycarbonate and poly (1,4-butylene terephthalate) in a weight ratio of 0:90,
The polymer composition according to claim 13. 16. The blend comprises from about 75:25 to about 2.
Consisting of bisphenol A polycarbonate and poly (1,4-butylene terephthalate) in a weight ratio of 5:75,
The polymer composition according to claim 13. 17. The polymer composition of claim 1, wherein the hindered amine is less than about 2.0% by weight, based on the total weight of polymer in the composition. 18. The polymer composition of claim 17, wherein the hindered amine is less than about 0.6% by weight, based on the total weight of polymer in the composition. 19. The polymer composition of claim 1, wherein the bis-alkyleneamino cyanoacrylate ester is less than about 2.0% by weight, based on the total weight of polymer in the composition. 20. The polymer composition of claim 19, wherein the bis-alkyleneamino cyanoacrylate ester is less than about 0.6% by weight, based on the total weight of polymer in the composition. 21. The polymer composition of claim 1, wherein the acrylic polymer is poly (methyl methacrylate).